Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines
- Autores
- Pieslinger, German Eduardo; Cadranel, Alejandro; Baraldo Victorica, Luis Mario
- Año de publicación
- 2020
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- This article discusses the use of density functional theory (DFT) calculations in classifying and characterizing bimetallic ruthenium mixed-valence systems in terms of their electronic localization/ delocalization degree. A standard B3LYP/LanL2DZ methodology including integral equation formalism-polarizable continuum model (IEF-PCM) solvent model is evaluated for a set of 16 nonsymmetric mixed-valence cyanide-bridged ruthenium polypyridines. This procedure reproduces well the features of the observed electronic and vibrational spectra, with better agreement for the more delocalized systems, and therefore provides an appropriate description of the electronic structures. Computed spin densities support class II or class III Robin-Day assignments and allow to quantify the electronic delocalization degree. The applied methodology yields good results due to the nature of the systems explored, which display a strong electronic coupling promoted by the cyanide-bridge and a lack of strong specific solvation effects. This procedure is not only useful in the study of ground state mixed-valence systems, but also provides a powerful insight into photoinduced mixed-valence excited states of related complexes.
Fil: Pieslinger, German Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas "Prof. Alejandro C. Paladini". Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Físico-Química Biológicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Cadranel, Alejandro. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universitat Erlangen Nuremberg; Alemania
Fil: Baraldo Victorica, Luis Mario. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina - Materia
-
CYANIDE-BRIDGE
DFT CALCULATIONS
ELECTRON TRANSFER
RUTHENIUM POLYPYRIDINES - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/142361
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Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium PolypyridinesPieslinger, German EduardoCadranel, AlejandroBaraldo Victorica, Luis MarioCYANIDE-BRIDGEDFT CALCULATIONSELECTRON TRANSFERRUTHENIUM POLYPYRIDINEShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1This article discusses the use of density functional theory (DFT) calculations in classifying and characterizing bimetallic ruthenium mixed-valence systems in terms of their electronic localization/ delocalization degree. A standard B3LYP/LanL2DZ methodology including integral equation formalism-polarizable continuum model (IEF-PCM) solvent model is evaluated for a set of 16 nonsymmetric mixed-valence cyanide-bridged ruthenium polypyridines. This procedure reproduces well the features of the observed electronic and vibrational spectra, with better agreement for the more delocalized systems, and therefore provides an appropriate description of the electronic structures. Computed spin densities support class II or class III Robin-Day assignments and allow to quantify the electronic delocalization degree. The applied methodology yields good results due to the nature of the systems explored, which display a strong electronic coupling promoted by the cyanide-bridge and a lack of strong specific solvation effects. This procedure is not only useful in the study of ground state mixed-valence systems, but also provides a powerful insight into photoinduced mixed-valence excited states of related complexes.Fil: Pieslinger, German Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas "Prof. Alejandro C. Paladini". Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Físico-Química Biológicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Cadranel, Alejandro. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universitat Erlangen Nuremberg; AlemaniaFil: Baraldo Victorica, Luis Mario. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaSociedade Brasileira de Química2020-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/142361Pieslinger, German Eduardo; Cadranel, Alejandro; Baraldo Victorica, Luis Mario; Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines; Sociedade Brasileira de Química; Journal of the Brazilian Chemical Society; 31; 11; 5-2020; 2360-23700103-50531678-4790CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.scielo.br/j/jbchs/a/5rr5sGdtV4ZwTs7GkC9DVKk/?lang=eninfo:eu-repo/semantics/altIdentifier/doi/10.21577/0103-5053.20200135info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:00:00Zoai:ri.conicet.gov.ar:11336/142361instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 10:00:01.149CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines |
title |
Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines |
spellingShingle |
Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines Pieslinger, German Eduardo CYANIDE-BRIDGE DFT CALCULATIONS ELECTRON TRANSFER RUTHENIUM POLYPYRIDINES |
title_short |
Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines |
title_full |
Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines |
title_fullStr |
Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines |
title_full_unstemmed |
Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines |
title_sort |
Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines |
dc.creator.none.fl_str_mv |
Pieslinger, German Eduardo Cadranel, Alejandro Baraldo Victorica, Luis Mario |
author |
Pieslinger, German Eduardo |
author_facet |
Pieslinger, German Eduardo Cadranel, Alejandro Baraldo Victorica, Luis Mario |
author_role |
author |
author2 |
Cadranel, Alejandro Baraldo Victorica, Luis Mario |
author2_role |
author author |
dc.subject.none.fl_str_mv |
CYANIDE-BRIDGE DFT CALCULATIONS ELECTRON TRANSFER RUTHENIUM POLYPYRIDINES |
topic |
CYANIDE-BRIDGE DFT CALCULATIONS ELECTRON TRANSFER RUTHENIUM POLYPYRIDINES |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
This article discusses the use of density functional theory (DFT) calculations in classifying and characterizing bimetallic ruthenium mixed-valence systems in terms of their electronic localization/ delocalization degree. A standard B3LYP/LanL2DZ methodology including integral equation formalism-polarizable continuum model (IEF-PCM) solvent model is evaluated for a set of 16 nonsymmetric mixed-valence cyanide-bridged ruthenium polypyridines. This procedure reproduces well the features of the observed electronic and vibrational spectra, with better agreement for the more delocalized systems, and therefore provides an appropriate description of the electronic structures. Computed spin densities support class II or class III Robin-Day assignments and allow to quantify the electronic delocalization degree. The applied methodology yields good results due to the nature of the systems explored, which display a strong electronic coupling promoted by the cyanide-bridge and a lack of strong specific solvation effects. This procedure is not only useful in the study of ground state mixed-valence systems, but also provides a powerful insight into photoinduced mixed-valence excited states of related complexes. Fil: Pieslinger, German Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas "Prof. Alejandro C. Paladini". Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Físico-Química Biológicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina Fil: Cadranel, Alejandro. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universitat Erlangen Nuremberg; Alemania Fil: Baraldo Victorica, Luis Mario. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina |
description |
This article discusses the use of density functional theory (DFT) calculations in classifying and characterizing bimetallic ruthenium mixed-valence systems in terms of their electronic localization/ delocalization degree. A standard B3LYP/LanL2DZ methodology including integral equation formalism-polarizable continuum model (IEF-PCM) solvent model is evaluated for a set of 16 nonsymmetric mixed-valence cyanide-bridged ruthenium polypyridines. This procedure reproduces well the features of the observed electronic and vibrational spectra, with better agreement for the more delocalized systems, and therefore provides an appropriate description of the electronic structures. Computed spin densities support class II or class III Robin-Day assignments and allow to quantify the electronic delocalization degree. The applied methodology yields good results due to the nature of the systems explored, which display a strong electronic coupling promoted by the cyanide-bridge and a lack of strong specific solvation effects. This procedure is not only useful in the study of ground state mixed-valence systems, but also provides a powerful insight into photoinduced mixed-valence excited states of related complexes. |
publishDate |
2020 |
dc.date.none.fl_str_mv |
2020-05 |
dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
format |
article |
status_str |
publishedVersion |
dc.identifier.none.fl_str_mv |
http://hdl.handle.net/11336/142361 Pieslinger, German Eduardo; Cadranel, Alejandro; Baraldo Victorica, Luis Mario; Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines; Sociedade Brasileira de Química; Journal of the Brazilian Chemical Society; 31; 11; 5-2020; 2360-2370 0103-5053 1678-4790 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/142361 |
identifier_str_mv |
Pieslinger, German Eduardo; Cadranel, Alejandro; Baraldo Victorica, Luis Mario; Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines; Sociedade Brasileira de Química; Journal of the Brazilian Chemical Society; 31; 11; 5-2020; 2360-2370 0103-5053 1678-4790 CONICET Digital CONICET |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/url/https://www.scielo.br/j/jbchs/a/5rr5sGdtV4ZwTs7GkC9DVKk/?lang=en info:eu-repo/semantics/altIdentifier/doi/10.21577/0103-5053.20200135 |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by/2.5/ar/ |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
https://creativecommons.org/licenses/by/2.5/ar/ |
dc.format.none.fl_str_mv |
application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
Sociedade Brasileira de Química |
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Sociedade Brasileira de Química |
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reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
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CONICET Digital (CONICET) |
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CONICET Digital (CONICET) |
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Consejo Nacional de Investigaciones Científicas y Técnicas |
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CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.mail.fl_str_mv |
dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar |
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13.13397 |